500768 A7 B7 五、發明說明〇 ) 發明所屬技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關一種新穎的工業上能簡略化步驟連續製 造末端單位之羥基含量較少而適用爲各種聚矽氧烷橡膠組 成物成分的有機聚矽氧烷橡膠之連續製造方法。 目前之技術及解決問題之發明 聚矽氧烷橡膠因具有優良之耐候性、電氣特性、低壓 縮永久變形、耐熱性、耐寒性等特性，故近年來開始廣泛 地使用於電子機器、汔車、建築、醫療、食品等領域上。 例如，作爲遙控器、打字機、文字處理機、電腦端末、樂 器等橡膠接觸鍵之接觸台、或建築用氣套、複寫機用定著 滾軸、顯像滾軸、轉印滾軸、靜電滾軸、給紙滾軸等各種 滾軸、或音響裝置等防震橡膠、或使用於電腦之c D用包 裝等用途。但隨著聚矽氧烷橡膠之需求日增’因此希望製 造出一種品質更安定、生產性更高之低成本的聚矽氧烷橡 膠。 經濟部智慧財產局員工消費合作社印製 爲了滿足需求，有機聚矽氧烷之連續製造方法的提案 如，特開昭5 3 - 9 9 3 0 0號公報所揭示，於鹼性及/ 或酸性反應觸媒存在下高粘性有機聚矽氧烷之連續聚合法 。雖然其中曾記載此方法能製造1 0〜數百萬c P之高粘 性有機聚矽氧烷，但未曾記載高於此粘度之生橡膠領域的 有機聚矽氧烷。 另外，有機聚矽氧烷之末端單位的構造與末端停止齊[J 之構造有關。但，有機聚矽氧烷之製造方法中’原料中所 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500768 A7 B7 五、發明說明（2 ) (請先閱讀背面之注音？事項再填寫本頁) 含之微量水分具末端停止劑作用，因此，會減少所希望末 W卓位而於所得有機聚砂氧院之末端單位形成羥基。而這 類具末端羥基之高分子量的有機聚矽氧烷橡膠與二氧化砂 等補強材混練以調製聚矽氧烷橡膠複合物時，會因有機聚 矽氧烷橡膠末端之羥基與二氧化矽表面的羥基之相互作用 ’經時產生橡膠複合物之皺化（Crepe hardening )變化。 又，此產生皺化之橡膠複合物於使用前會因所使用之2個 滾軸等而賦予的再度強力之剪斷力，故有需使其接近初期 狀態之問題。 因此’以有機聚矽氧烷橡膠作爲聚矽氧烷橡膠複合物 原料時，一般係希望末端單位爲三有機甲矽烷基。但如上 述般，現狀上會因預期外之因素而使末端單位生成羥基， 故製造上述有機聚矽氧烷橡膠時需降低羥基含量。 經濟部智慧財產局員工消費合作社印製 降低羥基含量之方法如特開昭6 0 — 2 0 2 1 2 4號 公報所揭不’爲了去除開始原料之環聚砂氧垸或作爲末端 停止劑的低分子量之線狀有機聚矽氧烷中的微量水分，而 預先利用分子篩等乾燥劑對這些原料進行乾燥之方法，但 ，此反應前處理操作會使過程煩雜化，且需定期交換乾燥 劑，故不符經濟效益。 另外，特開昭6 0 - 4 9 0 3 3號公報所揭示之降低 有機聚矽氧烷末端單位的羥基之方法爲，將三有機鹵化矽 烷及六有機二矽胺烷加入鹼性觸媒中使其中和的方法。即 ，有機聚矽氧烷中所殘存之鹼觸媒可被三有機鹵化矽烷中 和，此步驟中，例如有鹵素副產物生成時，因鹵素受六有 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500768 A7500768 A7 B7 V. Description of the invention 0) The technical field to which the invention belongs (please read the precautions on the back before filling this page) This invention is related to a novel industry that can simplify the steps to continuously manufacture terminal units with less hydroxyl content and is applicable Continuous production method of organic polysiloxane rubber containing various polysiloxane rubber composition components. The current technology and the invention of the problem-solving polysiloxane rubber has been widely used in electronic equipment, bicycles, and automobiles in recent years due to its excellent weather resistance, electrical characteristics, low compression set, heat resistance, and cold resistance. Construction, medical, food and other fields. For example, as a contact table for rubber contact keys of remote controllers, typewriters, word processors, computer terminals, musical instruments, etc., or air jackets for construction, fixing rollers for copying machines, development rollers, transfer rollers, electrostatic rollers Various rollers such as shafts, paper feed rollers, vibration-proof rubbers such as audio devices, or packaging for CDs used in computers. However, with the increasing demand for polysiloxane rubber ', it is desired to produce a low-cost polysiloxane rubber with more stable quality and higher productivity. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to meet the demand, a proposal for a continuous production method of organopolysiloxanes is disclosed in JP-A No. 5 3-9 9 3 0 0, which is alkaline and / or acidic. Continuous polymerization of highly viscous organopolysiloxane in the presence of a reaction catalyst. Although it has been described that this method can produce 10 to several million c P of highly viscous organopolysiloxane, it has not been described that the organopolysiloxane in the field of raw rubber with a viscosity higher than this. In addition, the structure of the terminal unit of the organic polysiloxane is related to the structure of the terminal stop [J]. However, in the manufacturing method of organic polysiloxane, the paper size in the raw materials is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 500768 A7 B7 V. Description of the invention (2) (Please read the Note? Please fill in this page again.) The trace amount of water contained in it has the function of a terminal stopper. Therefore, it will reduce the desired terminal position and form a hydroxyl group at the terminal unit of the obtained organic polyoxygen compound. When this kind of high molecular weight organic polysiloxane rubber with terminal hydroxyl group is mixed with reinforcing materials such as sand dioxide to prepare a polysiloxane rubber compound, the hydroxyl group and silicon dioxide at the end of the organic polysiloxane rubber will be mixed. The interaction of the hydroxyl groups on the surface causes a crepe hardening change of the rubber compound over time. In addition, the wrinkled rubber compound has a strong shearing force given by the two rollers and the like used before use. Therefore, it is necessary to make it close to the initial state. Therefore, when an organic polysiloxane rubber is used as the raw material of the polysiloxane rubber compound, it is generally desired that the terminal unit is a triorganosilyl group. However, as mentioned above, in the current situation, hydroxyl groups are generated in terminal units due to unexpected factors. Therefore, it is necessary to reduce the hydroxyl content when manufacturing the above-mentioned organic polysiloxane rubber. The method for reducing the hydroxyl content is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, as disclosed in JP-A-Sho 6 0 — 2 0 2 1 2 4 '. Low-molecular-weight linear organic polysiloxane containing trace amounts of moisture, and drying these materials with a desiccant such as molecular sieve in advance. However, this pre-reaction treatment operation will complicate the process and the desiccant needs to be exchanged regularly. Therefore, it is not consistent with economic benefits. In addition, the method disclosed in Japanese Patent Laid-Open No. 6 0-4 9 0 3 for reducing the hydroxyl group at the terminal unit of an organic polysiloxane is to add a triorganohalosilane and a hexaorganodisilazane to a basic catalyst. Ways to make it neutral. That is, the alkali catalyst remaining in the organopolysiloxane can be neutralized by the triorganohalogenated silane. In this step, for example, when halogen by-products are generated, the paper is subject to the Chinese National Standard (CNS) because of halogens. A4 size (210 X 297 mm) 500768 A7
五、發明說明（3 ) 機二矽胺烷所中和，故爲可使有機聚矽氧烷安定化之方法 。此方法雖能達成羥基減化之目的，但會有增加步驟及使 用鹵化矽烷而造成金屬設備腐蝕之問題。 (請先閱讀背面之注咅？事項再填寫本頁} 因此希望開發出一種於製造高聚合度有機聚矽氧烷（ 有機聚矽氧烷橡膠）時，能有效降低末端單位之羥基含量 且更有效的製造方法。 有鑑於此’本發明之目的爲提供一*種能局生產性、低 成本連續製造末端單位之羥基含量較少的有機聚矽氧烷橡 膠，且能以簡略化步驟進行製造的連續製造方法。 解決問題之方法及發明的實施形態 經濟部智慧財產局員工消費合作社印製 本發明者爲了完成上述目的有經專心檢討後發明，利 用使（A )下列一般式（1 )所示至少1種之環聚矽氧院 及（B )末端封止劑混合的第一步驟，以自然洗淨型連續 聚合機供給第一步驟所得（A )及（B )成分之混合物後 ，將（C )鹼性聚合觸媒連續供給此混合物使其混合，再 於低於常壓之減壓下以1 3 0〜2 5 0 t進行聚合的第二 步驟，其後連續添加能有效使第二步驟之反應物中的觸媒 中和之中和劑以結束聚合反應的第三步驟，又以加上由第 三步驟所得聚合物中連續去除聚合殘分之環聚矽氧烷及揮 發性成分的第四步驟爲佳之方式，能以簡單而無需對末端 單位幾乎不含羥基之有機聚矽氧烷橡膠進行前處理的步驟 ，高生產性、低成本地以簡化步驟連續從事更安定品質且 無設備腐蝕等問題之製造過程，而完成本發明。 -6 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 5007685. Description of the invention (3) The organic disilazane is neutralized, so it is a method for stabilizing the organic polysiloxane. Although this method can achieve the purpose of reducing hydroxyl groups, it has the problem of increasing the number of steps and the use of halogenated silanes to cause corrosion of metal equipment. (Please read the note on the back? Matters before filling out this page} Therefore, I hope to develop a kind of organic polysiloxane (organic polysiloxane rubber) that can effectively reduce the hydroxyl content of the terminal unit and make it more stable. An effective manufacturing method. In view of this, the object of the present invention is to provide a kind of organic polysiloxane rubber with low hydroxyl content in terminal units that can be produced continuously and at a low cost, and can be manufactured in simplified steps. The continuous manufacturing method. The method of solving the problem and the implementation form of the invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inventor has invented the invention in order to accomplish the above purpose. The first step of mixing at least one cyclopolysiloxane and (B) end-sealing agent is shown. After the mixture of (A) and (B) components obtained in the first step is supplied by a natural cleaning type continuous polymerization machine, the (C) The alkaline polymerization catalyst is continuously supplied to the mixture to be mixed, and then the polymerization is carried out at a pressure of lower than normal pressure at 130 to 250 t in the second step. After that, continuous addition is effective. The catalyst in the reactant in the second step neutralizes the neutralizer to complete the third step of the polymerization reaction, and adds the cyclopolysiloxane and the polymer residue obtained in the third step to continuously remove the polymerization residues and The fourth step of the volatile component is a better way. It can be carried out in a simple manner without the need for pretreatment of organic polysiloxane rubbers with almost no hydroxyl groups in the terminal units. The manufacturing process of the present invention is completed without quality problems such as equipment corrosion. -6-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 500768
五、發明說明（4 ) (式中，R 1、R 2分別爲非取代或取代之一價經基。η爲 3以上之整數。） 上述式（1 )之環聚矽氧烷中的R 1、R 2分別爲非取 代或取代之一價羥基，又以碳數1〜1 2，特別是1〜8 者爲佳，其具體例如，甲基、乙基、丙基等烷基、乙烯基 、烯丙基等鏈烯基、苯基、甲苯基等芳基、苯基乙基等芳 烷基、烷芳基及前述之基的部分或全部氫原子受鹵原子、 氰基等取代之氯甲基、三氟丙基、氰基乙基、α-氰基苯 基乙基等，其中又以甲基、苯基、乙嫌基、三氟丙基。η 爲3以上之整數，又以3〜8之整數爲佳。 因此，本發明係提供一種有機聚矽氧烷橡膠之連續製 造方法，其特徵係包，（I)使（Α)上述一般式（1) 所示至少一種之環聚矽氧烷及（Β )末端封止劑混合的第 一步驟，（I I )以自動洗淨型連續聚合機供給第一步驟 所得（A )及（Β )成分之混合物’再連續將（C )鹼性 聚合觸媒供給此混合物使其混合後’低於常壓之減壓下以 1 3 0〜2 5 0 〇C進行聚合的第三步驟，（I I I )其後 連續將能有效使前述觸媒中和之量的中和劑供給第二步驟 之反應物以結束聚合反應的第三步驟° 下面將更詳細說明本發明，即’本發明之有機聚矽氧 烷橡膠的連續製造方法之第一步驟爲’使下列一般式（1 )所示至少一種之環聚矽氧烷〔（A )成分〕及末端封止 劑〔（B )成分〕混合之步驟。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝--------訂--------- 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明p ) 一 WSiO)^ (1) (請先閱讀背面之注咅？事項再填寫本頁) (式中，R 1、R 2分別爲非取代或取代之一價羥基’ n爲 3以上之整數。） 上述式（1 )之環聚矽氧烷中的R 1、R 2分別爲非取 代或取代之一價羥基，又以碳數1〜1 2，特別是1〜8 者爲佳，其具體例如，甲基、乙基、丙基等烷基、乙烯基 、烯丙基等鏈烯基、苯基、甲苯基等芳基、苯基乙基等芳 烷基、烷芳基及前述之基的部分或全部氫原子受鹵原子、 氰基等取代之氯甲基、三氟丙基、氰基乙基、^一氰基苯 基乙基等，其中又以甲基、苯基、·乙烯基、三氟丙基。η 爲3以上之整數，又以3〜8之整數爲佳。 經濟部智慧財產局員工消費合作社印製 上述式（1 )之環聚砂氧院例如，六甲基環三砂氧院 、八甲基環四矽氧烷等二甲基矽氧烷環狀物、四甲基四乙 烯基環四矽氧烷等甲基乙烯基矽氧烷環狀物、八苯基環四 矽氧烷等二苯基矽氧烷環狀物、三甲基三氟丙基環三矽氧 烷等甲基三氟丙基矽氧烷環狀物等。其中就供給原料之容 易性觀點又以八甲基環四矽氧烷等二甲基矽氧烷環狀體爲 佳，又就作爲交聯點導入鏈烯基之觀點又以倂用甲基乙烯 基矽氧烷環狀物爲佳。這些環狀矽氧烷可單獨使用或2種 以上混合使用。 添加末端封止劑以停止聚合反應可調節重量平均分子 量。所使用之末端封止劑例如，乙烯基鏈鎖停止劑、甲基 鏈鎖停止劑等三烷基矽氧烷鏈鎖停止劑等已知鏈鎖停止劑 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 8 - 500768 A7 B7 五、發明說明（6 ) ’其具體例如下列式（2 )所示之物。又，可依最終生成 物之使用目的用途單獨使用1種或2種以上混合使用。本 發明又以甲基鏈鎖停止劑等三烷基矽氧烷鏈鎖停止劑或乙 烯基鏈鎖停止劑之含鏈烯基烷基矽氧烷鏈鎖停止劑特別佳5. Description of the invention (4) (In the formula, R 1 and R 2 are unsubstituted or substituted monovalent warp groups. Η is an integer of 3 or more.) R in the cyclopolysiloxane of formula (1) above 1. R 2 is an unsubstituted or substituted monovalent hydroxyl group, respectively, and it is preferably 1 to 12 carbon atoms, especially 1 to 8 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, and propyl, and ethylene. Alkenyl groups such as alkyl, allyl, aryl groups such as phenyl and tolyl, aralkyl groups such as phenylethyl, alkaryl groups, and some or all of the hydrogen atoms are replaced by halogen atoms, cyano groups, etc. Chloromethyl, trifluoropropyl, cyanoethyl, α-cyanophenylethyl, etc., of which methyl, phenyl, ethylthio, and trifluoropropyl. η is an integer of 3 or more, and an integer of 3 to 8 is more preferable. Therefore, the present invention provides a continuous manufacturing method of an organic polysiloxane rubber, which is characterized by (I) making (A) at least one cyclopolysiloxane represented by the general formula (1) and (B) In the first step of mixing the end-sealing agent, (II) The mixture of the components (A) and (B) obtained in the first step is supplied by an automatic cleaning type continuous polymerization machine, and then (C) the alkaline polymerization catalyst is continuously supplied to this. After the mixture is mixed, the third step of polymerization is carried out at a pressure of lower than normal pressure at 130 to 2500 ° C. (III) The subsequent steps will be effective to neutralize the amount of the catalyst. The third step is to supply the reactant in the second step to terminate the polymerization reaction. The present invention will be described in more detail below, that is, the first step of the continuous production method of the organic polysiloxane rubber of the present invention is to make the following general A step of mixing at least one cyclopolysiloxane [(A) component] and a terminal blocking agent [(B) component] represented by formula (1). This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page). -------- Order -------- -Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i. Invention Description p) a WSiO) ^ (1) (Please read the note on the back? Matters before filling out this page) (where R 1, R 2 Are unsubstituted or substituted monovalent hydroxyl groups' n is an integer of 3 or more.) R 1 and R 2 in the cyclopolysiloxane of formula (1) are unsubstituted or substituted monovalent hydroxyl groups, respectively, and The number of carbon atoms is from 1 to 12, especially from 1 to 8. Specific examples include alkyl groups such as methyl, ethyl, and propyl, alkenyl groups such as vinyl, allyl, and aromatic groups such as phenyl and tolyl. Aralkyl groups such as alkyl, phenylethyl, alkaryl, and some or all of the aforementioned hydrogen atoms are substituted by halogen atoms, cyano, etc. chloromethyl, trifluoropropyl, cyanoethyl, and cyano Examples include methylphenyl, methyl, phenyl, vinyl, and trifluoropropyl. η is an integer of 3 or more, and an integer of 3 to 8 is more preferable. The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above-mentioned cyclic polysand oxygen institutes of the formula (1). For example, hexamethylcyclotrisand oxygen institutes, dimethylsiloxane rings such as octamethylcyclotetrasiloxane, Methyl vinyl siloxane rings such as tetramethyl tetravinyl cyclotetrasiloxane, diphenyl siloxane rings such as octaphenyl cyclotetrasiloxane, trimethyl trifluoropropyl rings Methyltrifluoropropylsiloxane rings such as trisiloxane. Among them, dimethylsiloxane rings such as octamethylcyclotetrasiloxane and the like are preferred from the viewpoint of easiness of supplying raw materials, and methylethylene is used from the viewpoint of introducing an alkenyl group as a crosslinking point. The siloxane ring is preferred. These cyclic siloxanes can be used alone or in combination of two or more. Adding a terminal blocking agent to stop the polymerization reaction can adjust the weight average molecular weight. Used end-sealing agents, such as vinyl chain stoppers, methyl chain stoppers and other trialkylsiloxane chain stoppers and other known chain stoppers. This paper applies Chinese national standards (CNS) A4 specifications (210 X 297 mm) _ 8-500768 A7 B7 V. Description of the invention (6) 'The specific examples are as shown in the following formula (2). In addition, depending on the intended use of the final product, one type may be used alone or two or more types may be used in combination. The present invention is particularly preferably a trialkylsiloxane chain stopper such as a methyl chain stopper or an alkenyl alkylsiloxane chain stopper containing an ethylenic chain stopper.
上述式（2 )中，R 3〜R 8分別爲相同或相異之非取 代或取代1價羥基。此R 3〜R 8之1價羥基較佳爲，具上 述式（1)之R1、R2之碳數者，可用上述。R7、R8又 以甲基或乙烯基特別佳。η爲1〜2 0 0，又以1 0〜 1 0 0爲佳，特別佳爲2 0〜8 0之整數。 上述末端封止劑之添加量對式（1 )的環聚矽氧烷 1〇0單位（重量單位，以下均同）爲0 · 0 00 1〜 1〇單位，特別爲〇 · 〇 〇 〇 1〜5單位。 本發明之第一步驟中，可以任何方法使（A )成分之 上述式（1 )環聚矽氧烷及（B )成分的末端封止劑。 第一步驟中，混合（A)成分之環聚砂氧院及（B ) 成分的末端封止劑後，可於兩成分脫水、脫二氧化碳用N 2 氣體等不活性氣體之氣流下，利用矽膠或分子篩等進行乾 燥。 其次第二步驟中，以自動洗淨型連續聚合機供給第一 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) _ 裝--------訂--------- 經濟部智慧財產局員工消費合作社印製 -9 - 500768 五、發明說明（7 ) 步驟所得上述（A )、 （ B )成分之混合物，再連續將（ C )成分之鹼性聚合觸媒供給此混合物，低於常壓之減壓 下以1 3 0〜2 5 0°C進行聚合反應。 此時所使用之鹼性聚合觸媒例如，氫氧化鈉、氫氧化 鉀、氫氧化鉋等鹼金屬化合物、或其矽烷酸酯等，其中又 以鹼金屬氫氧化物之矽烷酸酯爲佳。又，這些鹼金屬化合 物或其矽烷酸酯可利用鹽酸、氯醇、醋酸、二氧化碳等酸 性中和劑使其中和、失活。本發明又以鹼金屬氫氧化物之 矽烷酸酯爲佳，特別佳爲氫氧化鉀之二甲基聚矽氧烷酸酯 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 第二步驟所使用之自動洗淨型 J S C R ( Self Cleaning Reactor ) 菱重工業（股）製）等。此SCR 字型剖面之筒狀的橫型容器，內設 個回轉軸2、 3 ，且各個回轉軸2 數厚肉型偏心圓板（回轉部）4、 轉軸2、3以等速度回轉時，相對 ，另一軸側連設的回轉部之相互的 與容器內壁會具有相對速度而移動 部內部的表面（「三菱聚工技法V ( 1 9 8 7 — 3 )」） 連續聚合機的具 或N — S 如圖1所 置相互以 、3中以 5 ，因此 的回轉部 側面、回 ’故可完In the above formula (2), R 3 to R 8 are the same or different non-substituted or substituted monovalent hydroxyl groups, respectively. The monovalent hydroxyl groups of R 3 to R 8 are preferably those having the carbon number of R1 and R2 of the formula (1), and the above can be used. R7 and R8 are particularly preferably methyl or vinyl. η is 1 to 2 0, and more preferably 10 to 1 0, particularly preferably an integer of 2 to 8 0. The added amount of the above-mentioned end-sealing agent is 0. 0 00 1 to 10 units, and particularly 0. 〇〇〇001, for 100 units (weight unit, hereinafter the same) of the cyclopolysiloxane of formula (1). ~ 5 units. In the first step of the present invention, the cycloaminopolysiloxane of the formula (1) and the terminal blocking agent of the component (B) of the component (A) can be produced by any method. In the first step, after mixing the (A) cyclohedral oxygen compound and the (B) terminal sealing agent, the two components can be dehydrated and carbon dioxide deactivated N 2 gas and other inert gases can be used to use silicone rubber. Or molecular sieve and the like. In the second step, the first paper size is supplied by the automatic cleaning continuous polymerization machine to the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back before filling this page) _ Packing -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -9-500768 V. Description of the invention (7) Steps (A) and (B) The mixture of ingredients is continuously supplied with the basic polymerization catalyst of the (C) ingredient, and the polymerization reaction is carried out at 130 to 250 ° C under reduced pressure below normal pressure. The alkaline polymerization catalyst used at this time is, for example, an alkali metal compound such as sodium hydroxide, potassium hydroxide, or hydroxide, or a silicate thereof. Among them, a silicate of an alkali metal hydroxide is preferred. These alkali metal compounds or their silicates can be neutralized and deactivated by acid neutralizing agents such as hydrochloric acid, chlorohydrin, acetic acid, and carbon dioxide. In the present invention, the alkanoate of alkali metal hydroxide is more preferred, and the dimethyl polysiloxane of potassium hydroxide is particularly preferred (please read the precautions on the back before filling this page). Bureau of Intellectual Property, Ministry of Economic Affairs The self-cleaning type JSCR (Self-cleaning Reactor) used by the employee consumer cooperative prints the second step. When the cylindrical horizontal container of the SCR-shaped cross section is provided with a rotary shaft 2, 3, and each rotary shaft 2 is a thick meat-shaped eccentric circular plate (rotary part) 4, and the rotary shafts 2 and 3 rotate at a constant speed, On the other hand, the surface of the rotating part connected to the rotating part connected to the other shaft side with the container inner wall will move at a relative speed ("Mitsubishi Polytechnique V (1 9 8 7 — 3)"). N — S, as shown in Figure 1, are placed on each other, and 3 out of 5, so the side of the turning part can be completed.
C R ( 示，係 同向回 螺旋狀 ，當此 之相互 轉部之 全洗淨 4 ， N )。此時，原料係由容器之一 容器內，容器內再以回轉部進行攪拌並朝長方向移 進行聚合反應，最後由容器另一端取出。但，回轉 方式非限於螺旋狀，可自由變化。 體例如 均爲三 於具8 轉的2 附著多 2個回 的外周 最外周 容器全 〇 . 2 端投入 動，以 部設置 -Ίυ _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500768 A7 ______W_______ 五、發明說明（8 ) 使用自動洗淨型連續聚合機時需低於常壓7 6 0 mmHg ’又以5 〇 OmmHg以下爲佳，更佳爲3 0〜 1 OOmmHg 下以 1 30 〜2 50 °C，又以 1 50 〜 2 0 0 °c爲佳進行聚合。經第二步驟可得末端單位之羥基 含量較少且具安定品質的高聚合度有機聚矽氧烷橡膠。又 ，一般於開始聚合時間會產生熱。至於聚合時間並無特別 限制，但一般爲0 · 5〜2小時。 因本發明方法係，低於常壓之壓力下進行目前於常壓 〜微加壓下進行的鹼性聚合觸媒之聚合步驟，故進行聚合 反應的同時可有效去除反應系內所存在的水分。若壓力高 於常壓時，將無法充分去除水分，而形成末端單位之羥基 ，因此無法達成本發明之目的。 連續供給能中和鹼性聚合觸媒之有效量的中和劑之第 三步驟，可直接使用第二步驟所使用的自動洗淨型聚合機 ，或使用另一擠押機。又，此擠押機較佳爲使用單軸、雙 軸或多軸擠押機其他連續處理裝置進行。 所得之有機聚矽氧烷橡膠可直接使用，但一般又以去 除殘存於所得有機聚矽氧烷橡膠中的低分子矽氧烷或觸媒 之分解副產物等揮發性物質者爲佳。因此，結束第三步驟 後，較好能進行連續去除所得聚合反應物中聚合聚存成分 之殘存環聚矽氧烷及揮發性成分的第四步驟。 此第四步驟又以使用單軸、雙軸或多軸擠押機、其他 連續處理裝置進行爲佳’特別佳係於連續去除聚合殘存成 分之環聚矽氧烷及揮發性成分的裝置途中或後方設置脫氣 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) 二1 1 _ (請先閱讀背面之注意事項再填寫本頁) 裝--------^訂---------. 經濟部智慧財產局員工消費合作社印製 500768 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明θ ) 口、薄膜型或細線型脫氣裝置者。· 一般第四步驟係於1 5 0〜2 5 0 °C，低於常壓之 7 6 0 m m H g下進行，又以儘可能之低操作壓力下進行 爲佳，必要時以具減壓操作之過程更佳。經第四步驟後可 減少所得有機聚矽氧烷橡膠中殘存之低分子矽氧烷、觸媒 之分解副產物等揮發性物質。 上述方法所得有機聚矽氧烷橡膠一般之平均聚合度爲 3，000以上，又以4，000以上者爲佳。此平均聚 合度並無上限限制，但一般爲3 0，0 0 0以下。 因所得有機聚矽氧烷橡膠之末端單位實質上均以來自 上述低分子量線狀有機聚矽氧烷末端之三有機甲矽烷基的 三有機甲矽烷基對鏈，故能明顯減少末端羥基量，其後述 之相對粘度比爲1 · 1 0以下，又以1 · 0 5以下爲佳。 相對粘度比： 將有機聚矽氧烷橡膠1 0 g溶解於曱苯9 0 g中，再 滴入數滴四甲氧基矽烷0 · 5 g及四丙基鈦酸酯。測定此 溶液之初期粘度及1小時後粘度，並算出其相對粘度比〔 1時後粘度/初期粘度〕。 〔實施例〕 . 下面將以實施例及比較例具體說明本發明，但非限於 此例。 〔實施例、比較例〕 使用圖2所示般連續實驗過程之設備，以表1所示之 ------Μ,---------------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -1T- 768 A7 B7 1、發明說明〇〇 ) 原料及條件連續製造有機聚矽氧烷橡膠，測定所得有機聚 砂氧烷橡膠的生橡膠特性。結果如表1所示。 又，以各別定量之齒輪唧筒連續供給作爲使用原料之 環聚矽氧烷、末端封止劑、聚合觸媒。 所使用之自動洗淨型連續聚合機爲s C R (三菱重工 業（股）製）。 所使用之第三步驟的擠押機爲K R C ((股）栗本鐵 工所製）。 另外，去除所得聚合物之低分子矽氧烷係利用連續的 細線流下式控制器。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ^3- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500768 A7B7 五、發明說明（11 )〔表1〕 經濟部智慧財產局員工消費合作社印製 實施例 比較例 1 2 3 1 2 有機聚矽氧烷供給速度(kg/Hf 20 20 20 20 20 乙烯基末端停止劑供給速度(kg/Hf 0.14 0.14 0.14 0.14 0.14 聚合觸媒 3%氫氧化鉀二甲基聚 5.4 5.4 5.4 5.4 5.4 矽氧烷酸酯(g/H) 原料中水分(ppm) 120 110 200 100 70 第二步驟 聚合機滯留時間(mm) 60 60 60 60 60 (聚合步驟） 聚合時壓力(mmHg) 200 100 50 常壓 常壓 聚合溫度ΓΟ 180 180 200 180 180 第三步驟 氯乙醇(g/H) 1.2 1.2 1.2 1.2 1.2 (中和步驟） 觸媒中和時間溫度 180 180 180 180 180 (°C) 觸媒中和時間(min) 60 60 60 60 60 去除低分子矽 溫度(。〇 200 200 — 200 200 氧烷 壓力(mmHg) 2 2 — 2 2 所得生橡膠之特性 數平均分子量 55萬 58萬 56萬 18萬 37萬 平均聚合度 7,3〇〇 7,700 7,400 2.300 4,800 相對粘度比” 1.02 10.1 1.02 1.20 1.11 備考 生橡膠 生橡膠 生橡膠 低聚合度 生橡膠 生橡膠 黏滯性 黏滯性 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14- 500768 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（12 ) * 1 : η = 3〜7之二甲基環矽氧烷混合物 ^(CH^.SiOhr- * 2 :末端以二甲基乙烯基封端之2 5 t：下粘度爲 6 〇 c s的直鏈狀二甲基聚矽氧烷 CH3 I 一 SiCH=CH2、…乂h3 (P係使2 5 t：下之粘度爲6 0 c S之數） * 3 :相對粘度比 將有機聚矽氧烷橡膠1 0 g溶解於甲苯9 0 g中，再 滴入數滴四甲氧基矽烷0 · 5 g及四丙基鈦酸酯。測定此 溶液之初期粘度及1小時後粘度，並算出其相對粘度比〔 • 1時後粘度/初期粘度〕。 當相對粘度比近似1時，因有機聚矽氧烷橡膠中幾乎 不存在羥基，故無需進行四甲氧基矽烷之甲氧基與羥基的 縮合反應，因此無粘度變化。 由表1內容得知，本發明製造法比起目前已知之技術 ，其連續聚合步驟無需複雜前處理脫水步驟，能以簡單步 驟連續地以簡化步驟製得末端單位之羥基含量減低化之高 聚合度的具安定品質之有機聚砂氧院橡膠。 故本發明可以低成本、高生產性地連續製造末端單位 之羥基含量減低化的高聚合度之具安定品質的有機聚矽氧 烷橡膠。 CH, CH2=CHSi-0 CH, CH3 I -SiO -I CH, (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 500768 A7 _ B7 五、發明說明（13 ) 〔圖面之簡單說明〕 圖1爲，自動洗淨型連續聚合機（s C R )之縱剖面 圖。 圖2爲，本發明之連續製造過程之一實施例的步驟圖 〔符號之說明〕 (請先閱讀背面之注意事項再填寫本頁) ---------訂--------- 1 橫型容器 2、3 回轉軸 4、 5 偏心圓板 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16-C R (shown as a spiral in the same direction, when the rotating parts are completely cleaned 4, N). At this time, the raw material is contained in one of the containers, and the container is stirred by the rotating part and moved in a long direction to perform the polymerization reaction, and finally taken out from the other end of the container. However, the rotation method is not limited to a spiral shape and can be freely changed. For example, the outermost outer container with three attachments and two attachments with 8 rotations and 2 backs is fully inserted at the 0.2 end, and is set by the department-Ίυ _ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 500768 A7 ______W_______ 5. Description of the invention (8) When using an automatic cleaning type continuous polymerization machine, the pressure should be lower than normal pressure 7 600 mmHg 'and preferably less than 500 mmHg, more preferably 30 to 100 mmHg The polymerization is preferably carried out at a temperature of 1 30 to 2 50 ° C, and preferably 1 50 to 2 0 ° C. After the second step, a highly polymerized organic polysiloxane rubber with less hydroxyl content in the terminal units and stable quality can be obtained. In addition, heat is generally generated at the start of polymerization. The polymerization time is not particularly limited, but it is generally from 0.5 to 2 hours. Because the method of the present invention, the polymerization step of the alkaline polymerization catalyst currently performed under normal pressure to a slight pressure is performed under a pressure lower than normal pressure, so the water existing in the reaction system can be effectively removed while the polymerization reaction is performed. . If the pressure is higher than normal pressure, the water cannot be removed sufficiently, and the hydroxyl groups of the terminal units are formed, so the purpose of the present invention cannot be achieved. In the third step of continuously supplying an effective amount of a neutralizing agent capable of neutralizing the alkaline polymerization catalyst, the automatic washing type polymerization machine used in the second step can be directly used or another extruder can be used. In addition, the extruder is preferably carried out using a single-axis, twin-axis, or multi-axis extruder or other continuous processing device. The obtained organic polysiloxane rubber can be used directly, but it is generally better to remove volatile substances such as low-molecular-weight siloxane or catalyst decomposition by-products remaining in the obtained organic polysiloxane rubber. Therefore, after the third step is completed, it is preferable to be able to perform the fourth step of continuously removing the residual cyclopolysiloxane and volatile components of the polymerized components in the obtained polymerization reaction product. This fourth step is preferably performed by using a single-axis, dual-axis or multi-axis extruder, other continuous processing equipment. It is particularly good in the device that continuously removes the polysiloxane and the volatile components of the polymer remaining components or Degassing is set at the back. This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 public love). 2 1 1 _ (Please read the precautions on the back before filling this page). Loading -------- ^ Order ---------. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by 500768 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 5. Description of the invention θ) Mouth, film or thin line degassing device By. · Generally, the fourth step is performed at 150 ~ 250 ° C, which is lower than 760 mm H g of normal pressure, and it is better to perform at the lowest operating pressure possible, and if necessary, reduce the pressure The process is better. After the fourth step, the low-molecular-weight siloxanes remaining in the obtained organopolysiloxane rubber and the volatile substances such as decomposition byproducts of the catalyst can be reduced. The organic polysiloxane rubber obtained by the above method generally has an average degree of polymerization of 3,000 or more, and more preferably 4,000 or more. There is no upper limit to the average degree of polymerization, but it is generally below 30,00. Since the terminal units of the obtained organic polysiloxane rubbers are all substantially linked by the triorganosilyl groups derived from the triorganosilyl groups at the ends of the low molecular weight linear organic polysiloxane, the amount of terminal hydroxyl groups can be significantly reduced. The relative viscosity ratio described later is preferably 1 · 10 or less, and more preferably 1 · 0 5 or less. Relative viscosity ratio: 10 g of organopolysiloxane rubber was dissolved in 90 g of toluene, and several drops of tetramethoxysilane 0.5 g and tetrapropyl titanate were added dropwise. The initial viscosity and the viscosity after 1 hour of this solution were measured, and the relative viscosity ratio [viscosity after 1 hour / initial viscosity] was calculated. [Examples] The present invention will be specifically described with reference to examples and comparative examples, but is not limited to this example. [Examples and Comparative Examples] The equipment used in the continuous experimental process shown in Fig. 2 is shown in Table 1 ------ M, ---------------- ( Please read the notes on the back before filling in this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -1T- 768 A7 B7 1. Description of the invention 〇) Raw materials and conditions for continuous organic production Polysiloxane rubber, and the raw rubber characteristics of the obtained organic polysand siloxane rubber were measured. The results are shown in Table 1. In addition, cyclic polysiloxanes, terminal sealants, and polymerization catalysts as raw materials are continuously supplied in gear drums of respective amounts. The automatic cleaning type continuous polymerization machine used is s C R (Mitsubishi Heavy Industries, Ltd.). The extruder used in the third step was K R C (made by Kurimoto Iron Works). In addition, the low-molecular-weight siloxane system from which the obtained polymer was removed was a continuous thin-line flow-down controller. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 3- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 500768 A7B7 V. Invention Explanation (11) [Table 1] Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Comparative Example 1 2 3 1 2 Supply rate of organic polysiloxane (kg / Hf 20 20 20 20 20 Supply rate of vinyl terminal stopper) (kg / Hf 0.14 0.14 0.14 0.14 0.14 Polymerization catalyst 3% Potassium hydroxide dimethyl poly 5.4 5.4 5.4 5.4 5.4 Siloxane (g / H) Moisture in raw materials (ppm) 120 110 200 100 70 Second step Polymerizer residence time (mm) 60 60 60 60 60 (polymerization step) Pressure during polymerization (mmHg) 200 100 50 Normal pressure and normal pressure polymerization temperature ΓΟ 180 180 200 180 180 Third step chloroethanol (g / H) 1.2 1.2 1.2 1.2 1.2 (Neutralization step) Catalyst neutralization time temperature 180 180 180 180 180 (° C) Catalyst neutralization time (min) 60 60 60 60 60 Temperature for removing low molecular silicon (.200 200 — 200 200 Oxane Pressure (mmHg) 2 2 — 2 2 The average molecular weight is 55,558,560,18,370,370,000. The average degree of polymerization is 7,300,700, 7,400, 2,300, 4,800. Relative viscosity ratio "1.02 10.1 1.02 1.20 1.11 Candidate rubber Raw rubber Raw rubber Raw rubber Raw rubber Viscosity Viscosity (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -14- 500768 A7 B7 Employees ’Intellectual Property Bureau Printed by the cooperative V. Description of the invention (12) * 1: dimethylcyclosiloxane mixture with η = 3 ~ 7 ^ (CH ^ .SiOhr- * 2: 2 5 t terminated with dimethyl vinyl end : Linear dimethylpolysiloxane CH3 I-SiCH = CH2, ... 乂 h3 with a lower viscosity of 60 ° C (P is 2 5 t: the lower viscosity is 60 0 c S) * 3: Relative viscosity ratio: 10 g of an organopolysiloxane rubber was dissolved in 90 g of toluene, and several drops of tetramethoxysilane 0.5 g and tetrapropyl titanate were added dropwise. The initial viscosity and the viscosity after 1 hour of this solution were measured, and the relative viscosity ratio [• viscosity at 1 hour / initial viscosity] was calculated. When the relative viscosity ratio is approximately 1, since there is almost no hydroxyl group in the organopolysiloxane rubber, the condensation reaction between the methoxy group of the tetramethoxysilane and the hydroxyl group is not required, so there is no change in viscosity. From the contents of Table 1, it is known that compared with the currently known technology, the production method of the present invention does not require a complicated pretreatment dehydration step in the continuous polymerization step, and can continuously obtain a high polymerization with a reduced hydroxyl content in the terminal unit by a simple step and a simplified step. Degree of stability of organic polysand oxygen hospital rubber. Therefore, the present invention can continuously produce low-cost, high-productivity organic polysiloxane rubber with stable quality and a high degree of polymerization in which the hydroxyl content of the terminal unit is reduced. CH, CH2 = CHSi-0 CH, CH3 I -SiO -I CH, (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- 15- 500768 A7 _ B7 V. Description of the invention (13) [Simplified description of the drawing] Fig. 1 is a longitudinal sectional view of an automatic cleaning type continuous polymerization machine (s CR). Figure 2 is a step diagram of an embodiment of the continuous manufacturing process of the present invention [Explanation of symbols] (Please read the precautions on the back before filling out this page) --------- Order ----- ---- 1 Horizontal container 2, 3 Rotary axis 4, 5 Eccentric circular plate Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) -16 -